TEST METHODS

&
INSTRUMENTS
by
Gieva Salibongcogon
Pollution Control Engineer
Tests

■ pH
■ Specific Gravity
■ Oxidation-Reduction Potential
pH
■ Colorimetric
– The principle of colorimetric
determination of the pH value is based
on the pH dependence of color change

■ Potentiometric
– The principle of potentiometric pH
measurement can be explained by
Nernst’s law (potential difference).
 Colorimetric

• The basis for colorimetric analysis is

the variation in the intensity of the
color of a solution with changes in pH.

• inherent property of the constituent

itself
• formation of a colored compound as
the result of the addition of a suitable
reagent (e.g. indicator)
 Colorimetric
pH indicator

• a halochromic chemical compound

added in small amounts to a solution
so the pH of the solution can be
determined visually
• has a specific pH range over which it
changes from its acid form to its
base form

practicality:
not useful outside its pH range because
the indicator does not change color
over these pH values
 Colorimetric
pH test papers or strips

• Litmus Paper
o the most familiar pH paper used to
broadly test whether a solution is
acidic or basic
• pH Strips
• has a large selection from wide pH
range, low sensitivity to narrow pH
range, high sensitivity

practicality:
give more accuracy and precision
than liquid indicators but still
inferior to pH meter
 Potentiometric

• pH meters measure a solution's pH by

measuring the electrical potential
difference between the pH electrode
and a reference electrode.

• inherent property of the constituent

itself
• formation of a colored compound as
the result of the addition of a suitable
reagent (e.g. indicator)
 Potentiometric
pH meter

• Handheld or Portable pH meter

o great for field work or quick pH
checks in a lab
• Bench pH meter
• are typically more precise and offer
more testing options

practicality:
gives the most accurate and
precise measurement
Specific Gravity

■ Gravimetric Method
– depends on the comparison of the
weights of equal volume of a liquid and
of water

■ Floating Spindle Method

– depends on the comparison of the
volumes of equal weights of a liquid
and of water
 Gravimetric

• consists of the following steps:

• weighing equal volumes of the liquid
at a known temperature and of water
at this or some other known
temperature
• calculating the ratio between these
two weights, denoting the weight of
water

Practicality:
more accurate
 Floating
Spindle
• based on the principle that a body
floating in a liquid displaces a volume
equal to its own weight

Practicality:
of sufficient accuracy for all practical
purposes
 Floating Spindle

• Hydrometer

• device used to determine directly the

specific gravity of a liquid

• usually consists of a thin glass tube

closed at both ends, with one end
enlarged into a bulb that contains fine
lead shot or mercury to cause the
instrument to float upright in a liquid
 Floating Spindle
Scale

• Hydrometer

• consists of 2 parts:
o Stem
 Scale
• Is calibrated by which the
specific gravity of the test Ballast
liquid is measured
o Bulb
 Ballast Glass Bead
• weights the hydrometer in
the liquid
 Glass Bead
• serves to buffer the
hydrometer
 USING A HYDROMETER
1. Before you use the hydrometer, make sure it is clean by
rinsing it in distilled water. Any residue may render a false
measurement.
2. To use the hydrometer, hold it by the stem so that the ballast
hangs below.
3. Gradually immerse the bulb into the center of the test liquid
until the surface level directly contacts the stem. Never drop
the hydrometer into the test liquid; it can damage the
hydrometer rendering a false measurement.
4. Gently release the stem.
5. Once the hydrometer is balanced (no longer bobbing up and
down), you may read the specific gravity.
6. You should notice that the surface level of the liquid is, in
fact, curved up along the edges of the liquid's container. This
effect is called a meniscus.
7. Locate where the meniscus is at its lowermost point along
the scale of the stem. Record the corresponding number
from the scale. This measurement is the density (g/mL) of
the liquid.
READING A HYDROMETER
READING A HYDROMETER
ORP

■ Potentiometric
– ORP is the direct measurement of
electrons in transit during Oxidation-
Reduction reactions
■ under oxidizing conditions, the
measuring probe loses electrons to the
solution, which creates a positive
potential;
■ in a reducing environment, electrons
are donated to the probe, producing a
negative potential.
ORP
• a typical industrial ORP measurement loop is similar to that
used for pH measurement.
• It includes a high input impedance analyzer, a reference
electrode, measuring electrode, and system ground.
 ORP Meter
• a millivolt meter, measuring very tiny
voltages generated across a circuit
formed by a measuring electrode (the
positive pole of the circuit normally
platinum), and a reference electrode (the
negative pole), with the process solution
in between.

• The difference in voltage between the

two electrodes is what is actually being
measured by the analyzer.
Calibration of pH and
ORP meter
Why Calibrate?

• To minimize any uncertainty in measurements

while ensuring precision and consistency

• The accuracy of all measuring devices degrade over time.

• Accurate measuring devices improve product quality.

Instrument Calibration is done to…

• Test new instruments and equipment

• Test instrument accuracy after repair or modification
• Verify measurements of instruments that correct bias or
instruments that are used as surrogates for other measurements
• Ensure accuracy during instrument application
• Ensure smooth functioning of equipment after scheduled usage
time has lapsed
• Stabilize effects of shock or exposure to adverse conditions
• Minimize effects of environmental changes, for e.g. - weather
changes
Risk involved in not calibrating an instrument

• Safety Procedure
• Wastage
• Faulty or Questionable Quality
• Fines or Litigations
• Increased Downtime
When to Calibrate?

The schedule for instrument calibration is dependent on:

• Use of the instrument
• Frequency of use
• Type of instrument
• Environment
• Level of Accuracy required
Benefits of regular instrument calibration

• Regulate and monitor the functioning of your equipment and

guarantees accuracy in the final output, while ensuring
instrument reliability
• Avoid production of faulty or questionable finished goods
• Adhere to the various government and industry standards, and be
on top of matters during inspections and checks
• Chances of discovering irregularities in your production process
• Reduces chances of false passes and false failures, allowing to
maintain the quality of final output
• Ensure your equipment is always working at its optimal capacity
while adhering to industry standards
pH Sensor Calibration

• Materials needed:
• pH meter
• Distilled water
• Beakers
• pH 7 buffer, a solution whose pH is constantly 7
• pH 4 buffer, a solution whose pH is constantly 4
• pH 9.21 buffer, a solution whose pH is constantly 9.21 (optional)
• Tissue (specifically for laboratory use)
Tips to produce good calibration

1. Before starting a calibration, make sure the electrode system is properly

cleaned so that the electrodes are fully functional. They must then be rinsed
with clean water to avoid contamination of the calibration solution(s).
2. Always use fresh buffer solutions to avoid the possibility of introducing errors
from contaminated or old solutions. Buffers supplied as liquids have a limited
shelf life, especially alkaline buffers, which absorb CO2 from the air.
3. NIST (primary) buffer standards are strongly recommended in order to ensure
the best accuracy and best buffer capacity is available. Commercially
adjusted buffers (e.g. 7.00, 9.00 or 10.00 pH) are a compromise as a
standard, and are often supplied without the temperature dependency curve.
Their stability will never be as good as NIST solutions.
3 Ways to Calibrate:
Automatic calibration
Some analyzers offer internally
programmed buffer tables, to
calculate the buffer value at the
actual temperature during the
calibration. In addition, the
stability of the reading is
automatically calculated, and when
the reading has stabilized fully
automatic adjustments of slope and
asymmetry are made. This
eliminates the question of how long
the operator should allow prior to
adjustment. A menu driven prompt
system conducts the operator
through the simple, foolproof
routine.
Manual calibration
This method lets the operator decide
the actual pH value to enter. Manual
calibration is most often used for
singlepoint adjustment of the
asymmetry potential, by comparison
method (grab sample). Manual
calibration can also be used to
perform a full 2-point calibration
with solutions other than the NIST
buffers that are listed in the
calibration tables. In this case, the
solutions are applied sequentially as
in the AUTOCAL method, but the user
determines the adjustment of
reading and stability.
Sample calibration
The operator activates the “SAMPLE”
calibration routine, at the same time
as taking a representative process
sample. After determining the pH of
this sample by independent methods,
(in the lab for example) the reading
can be adjusted in the analyzer.
While the sample is being analyzed,
the analyzer holds the sample data in
memory, while continuing to
control and read pH normally.
General Calibration Steps:
1. Rinse the electrodes thoroughly with distilled water to remove any remaining
cleaning solution.
2. Immerse the electrodes in the first buffer solution (usually the neutral buffer)
and stir the electrode for a few seconds to ensure that the gel layer of the pH
glass membrane is completely wetted by buffer solution and all other fluids are
removed.
3. Keep the electrode still let the measurement stabilize. For a good calibration
we advice to avoid any contact of the glass membrane with bottom of the
calibration vessel.
4. Adjust the meter reading to the pH value of the buffer solution according to
the method selected (automatic or manual).
5. Rinse the electrodes with tap water to remove the traces of the first buffer.
Then, immerse the electrodes in the second buffer solution (e.g. 4.01 or 9.18
depending on the measuring range) and repeat step 1.
6. Adjust the analyzer reading to the pH value of the buffer solution according to
the method selected (automatic or manual).
ORP Sensor Calibration

• Materials needed:
• ORP meter
• Distilled water
• Beakers
• pH 7 buffer, a solution whose pH is constantly 7
• pH 4 buffer, a solution whose pH is constantly 4
• pH 9.21 buffer, a solution whose pH is constantly 9.21 (optional)
• Quinhydrone
• Wood applicator
• Tissue (specifically for laboratory use)
Tips to produce good calibration

1. Before starting a calibration, make sure the electrode system is

properly cleaned so that the electrodes are fully functional. They must
then be rinsed with clean water to avoid contamination of the
calibration solution(s).
2. The buffer / Quinhydrone mixtures should be freshly made each time
the ORP electrodes are calibrated. Do not store the mixtures or use
after 2 hours as their values change with time.
3. NIST (primary) buffer standards are strongly recommended in order to
ensure the best accuracy and best buffer capacity is available.
Commercially adjusted buffers (e.g. 7.00, 9.00 or 10.00 pH) are a
compromise as a standard, and are often supplied without the
temperature dependency curve. Their stability will never be as good as
NIST solutions.
2 Ways to Calibrate:
Automatic calibration
Some analyzers offer internally
programmed buffer tables, to
calculate the buffer value at the
actual temperature during the
calibration. In addition, the
stability of the reading is
automatically calculated, and when
the reading has stabilized fully
automatic adjustments of slope and
asymmetry are made. This
eliminates the question of how long
the operator should allow prior to
adjustment. A menu driven prompt
system conducts the operator
through the simple, foolproof
routine.
Manual calibration
This method lets the operator decide
the actual pH value to enter. Manual
calibration is most often used for
singlepoint adjustment of the
asymmetry potential, by comparison
method (grab sample). Manual
calibration can also be used to
perform a full 2-point calibration
with solutions other than the NIST
buffers that are listed in the
calibration tables. In this case, the
solutions are applied sequentially as
in the AUTOCAL method, but the user
determines the adjustment of
reading and stability.
Sample calibration
The operator activates the “SAMPLE”
calibration routine, at the same time
as taking a representative process
sample. After determining the pH of
this sample by independent methods,
(in the lab for example) the reading
can be adjusted in the analyzer.
While the sample is being analyzed,
the analyzer holds the sample data in
memory, while continuing to
control and read pH normally.
Calibration Steps:

1. Fill a beaker with de-ionized or distilled water to use for rinsing

the electrode.
2. Fill a second beaker with pH 7 buffer to approximately ½ oz mark
and label the beaker pH 7.
3. Add to this buffer enough Quinhydrone that stays on about ¼ inch
long (6mm) of the wood applicator.
4. Use the wood applicator to stir the Quinhydrone into the buffer.
5. A small amount of Quinhydrone MUST remain un-dissolved; if all
the Quinhydrone dissolves add a small amount and stir. Repeat as
necessary until a small amount of Quinhydrone remains un-
dissolved.
Calibration Steps:

6. Fill a third beaker with pH 4 buffer to approximately ½ oz mark

and label the beaker pH 4.
7. Add to this buffer enough Quinhydrone that stays on about ¼ inch
long (6mm) on the wood applicator.
8. Use the wood applicator to stir the Quinhydrone into the buffer.
9. A small amount of Quinhydrone MUST remain un-dissolved; if all
the Quinhydrone dissolves add a small amount and stir. Repeat as
necessary until a small amount of Quinhydrone remains un-
dissolved.
10.Rinse the ORP electrode and pat it dry with a soft tissue.
Calibration Steps:

11.Put the electrode in the pH 7 mixture and stir the electrode

gently.
12.Allow the reading to stabilize, this typically takes 30 to 60
seconds, and note the reading.
13.The reading should be within about ±15mV from the following
values:
Calibration Steps:

14.Rinse the ORP electrode and pat it dry with a soft tissue.
15.Put the electrode in the pH 4 mixture and stir the electrode
gently.
16.Allow the reading to stabilize, this typically takes 30 to 60
seconds, and note the reading.
17.Add 170mV and 185mV to the reading from step 12. Write down
the calculated values.
Calibration Steps:
18. The reading should be between the two calculated values from step 17.
19. With time and/or use, the value in the pH 7 mixture may change,
however the reading from the pH 4 mixture must be within the two
calculated values (step 17). If the reading is within the range, it means
that the electrode has good span and should be able to be calibrated
along with the meter to reflect the proper ORP potential.
20. If the reading (step 16) is less than the calculated value, pH 7 mixture
value + 170mV (260mV), the electrode may be coated. Remove the
coating using the following suggestions. If the reading is still less than
the calculated value after cleaning, replace the electrode.
• Wipe the surface clean with a soft cloth or tissue.
• Soak the electrode in a chemical known to dissolve the suspected coating
material.
• Very gently polish the surface with a paper towel.
• After cleaning, let the electrode soak in one of the calibrating solutions for
about five minutes.
Calibration Steps:

21.If the reading (step 16) is more than the calculated value, pH 7
mixture value + 185mV (275mV), replace the electrode.
22.Once the ORP electrode is verified and is in good working order
put the electrode into the pH 7 mixture.
23.Follow the ORP meter calibration procedure to calibrate the ORP
value to one of the values in Table 1.